Pigment Identification

Survey of chemical substances in
consumer products
no. 48 2004
Survey and assessment of chemical

substances in window colours
Sonja Hagen Mikkelsen, Sven Havelund and Anders Skibsted

Mogensen, COWI A/S
Contents
PREFACE
LIST OF ABBREVIATIONS
HAZARD SYMBOLS AND R-PHRASES USED
SUMMARY AND CONCLUSIONS
INTRODUCTION
13
PIGMENTS
PAINT BINDERS
VEHICLE
ADDITIVES
SURVEY OF MANUFACTURERS AND SUPPLIERS

3.1 MANUFACTURERS
3.2
SUPPLIERS
3.3 WINDOW COLOURS
4 SURVEY OF CONSTITUENT SUBSTANCES IN WINDOW

COLOURS
4.1
4.2
4.3
4.4
PIGMENTS
PAINT BINDERS
MEDIUM
ADDITIVES
CHEMICAL ANALYSIS
5.1 TEST PRODUCTS
5.2 METHODS OF ANALYSIS
5.2.1 GC/MS screening (extractable organic substances)
5.2.2 X-ray analysis (elements)
5.2.3 Water content using Karl Fisher titration
5.2.4 IR screening
5.3 ANALYSIS RESULTS
5.4 SUMMARY OF ANALYSIS
SELECTED SUBSTANCES AND DATA SEARCHING

6.1 BASIS FOR THE SELECTION OF SUBSTANCES
6.2 THE SELECTED SUBSTANCES
6.3 DATA SEARCH
9
9
9
10
2.1
2.2
2.3
2.4
6
6
SURVEY
CHEMICAL ANALYSIS
HEALTH EVALUATION
2 COMPOSITION OF AND TYPICAL CONSTITUENT

SUBSTANCES IN HOBBY PAINTS
TOXICOLOGICAL PROFILE OF SELECTED SUBSTANCES

7.1 TOXICOLOGICAL PROFILE OF 1-NAPHTHOL
7.1.1 Identification of the substance and physical-chemical properties
15
15
15
15
16
17
17
17
18
19
20
22
23
23
27
27
27
27
27
28
28
28
28
31
33
33
33
34
37
37
37
7.1.2 Toxicological properties

7.1.3 Conclusion
7.2 TOXICOLOGICAL PROFILE OF DIOXAZINE
7.2.3 Conclusion
7.3 TOXICOLOGICAL PROFILE OF DIMETHYLOXAZOLIDINE
7.3.3 Conclusion
7.4 TOXICOLOGICAL PROFILE FOR ETHYLMETHYLPYRIDINE
7.4.3 Conclusion
7.5 TOXICOLOGICAL PROFILE FOR METHYLBENZENESULFONAMIDE
7.5.3 Conclusion
7.6 TOXICOLOGICAL PROFILE OF METHENAMINE
7.6.3 Conclusion
7.7 TOXICOLOGICAL PROFILE OF DODECANTHIOL
7.7.3 Conclusion
7.8 TOXICOLOGICAL PROFILE OF 2-ETHYLHEXYLACRYLATE
7.8.3 Conclusion
7.9 TOXICOLOGICAL PROFILE OF PIGMENT RED 146
7.9.3 Conclusion
7.10 TOXICOLOGICAL PROFILE OF PIGMENT YELLOW 138
7.10.3 Conclusion
7.11 SUMMARY
8
REFERENCES
OTHER LITERATURE AND DATABASES CONSULTED:
38
40
40
40
41
42
42
42
43
44
44
44
45
45
45
45
46
46
47
47
48
52
52
52
53
53
54
54
55
57
58
58
59
59
59
59
60
60
60
64
65
PREFACE
The Danish EPA has undertaken an initiative to examine consumer exposure
to chemical substances in consumer products and the associated risks. A
variety of different product categories are involved including window colours
for hobby use, which are the object of the present report.
The object of the project is to carry out a survey of the constituent ingredients
of water-based window colours, both those which are CE marked and those
which are not. The survey is based on information from producers, suppliers
and independent consultants.
Yet another object is to carry out a human toxicological evaluation of selected
substances in the products and, if possible, give an estimate of the extent of
consumer exposure to these products. The human toxicological evaluation
was undertaken with a view to producing input for a possible subsequent risk
assessment with emphasis on the possible exposure of children to these
substances.
Moreover, the project is aimed at documenting the content of selected
chemical substances through chemical analysis of a number of products to be
found in the market. Finally, the purpose was to assess the need for further
chemical analysis based on the results produced.
The project report "Examination and Evaluation of Chemical Substances in
Window Paints" contains a review of the producers whose products are
available on the Danish market, the most important suppliers of these
products and of the products available on the Danish market.
The constituent substance are presented in table form classified as
pigments, vehicles and additives. The chemical name, chemical formula, CAS
no. and selected physical properties are given for each substance.
The project was initiated in November 2001. The first stage was completed in
December 2001 and the second in June 2003.
The project was carried out by COWI. MILJ-KEMI Dansk Milj Center
A/S, now named Eurofins Danmark A/S carried out analysis on selected
window colours. The project team consisted of Sonja Hagen Mikkelsen
(project officer), Sven Havelund, Anders Skibsted Mogensen and Frank
Stuer-Lauridsen (quality assurance).
The contact person at the Danish EPA was Shima Dobel, Chemicalsdivision,
The Consumer Section.
During the hearing Panduro have pointed out that the product SunArt
manufactured by Palmer Paint Products cannot be described as a window
paint. The product is a very thin fluid paint, which may be used on glass or
acrylic.
List of abbreviations
CAS no.
C.I. no.
Kow
LC 50
LD50
MW
NOAEL
S
Chemical Abstracts Service Registry number

Colour Index number
Octanol-Water Partition Coefficient
The concentration of a chemical that results in the death of
50% of test animals (Lethal Concentration)
The dose of a chemical that results in the death of 50% of test
animals (Lethal Dose)
Molecular Weight
No observed adverse effect level (the greatest amount of
chemical that produces no detectable effects on the test
animals)
Solubility
Hazard symbols and R-phrases used

Hazard symbols
F
Highly flammable
Xi
Local irritant
Xn
Harmful to health
C
Corrosive
N
Dangerous to the environment
R-phrases
R10
R11
R20
R21
R22
R23
R24
R25
R34
R36
R37
R38
R40
R41
R42
R43
R50
R51
R52
R53
Flammable
Highly flammable
Harmful by inhalation
Harmful in contact with skin
Harmful if swallowed
Toxic by inhalation
Toxic in contact with skin
Toxic if swallowed
Causes burns
Irritating to eyes
Irritating to respiratory system
Irritating to skin
Possible risk of cancer
Risk of serious damage to eyes
May cause sensitization by inhalation
May cause sensitization by skin contact
Very toxic to aquatic organisms
Toxic to aquatic organisms
Harmful to aquatic organisms
May cause long-term adverse effects in the aquatic environment
Combinations of R-phrases
R20/21/22
Harmful by inhalation, in contact with skin and if swallowed
R21/22
Harmful in contact with skin and if swallowed
R23/24/25
Toxic by inhalation, in contact with skin and if swallowed
R36/38
Irritating to eyes and skin
R36/37/38
Irritating to eyes, respiratory system and skin
Combinations of R-phrases
R37/38
Irritating to respiratory system and skin
R42/43
May cause sensitization by inhalation and skin contact
R51/53
Toxic to aquatic organisms; may cause long-term adverse effects in
the aquatic environment
R52/53
Harmful to aquatic organisms; may cause long-term adverse effects
in the aquatic environment
Summary and conclusions
Survey
Window coulours are a hobby product used by children and adults. CE
marked products are intended for children under the age of 14. CE marked
products must conform with the current regulations applying to toys and are
subject to restrictions with regard to the content and emission of substances
harmful to health. As not all consumers are familiar with the marking, the
Danish EPA assesses that children below the age of 14 will be at risk of
coming into contact with window colours that are not CE marked and which
do not comply with the current regulations for toys.
Exposure to substances contained in the products may occur by direct contact
with fingers, hands and face, and to some extent by inhalation.
As a consequence, there is a need to chart the substances that consumers may
be exposed to during use.
Worldwide, there are approximately 15 window paint producers and most
producers products are also available on the Danish market. Most of the
products are CE marked or bear other types of marking such as, for
example, the American AP Non Toxic mark, which is allocated to arts and
1
crafts materials that are certified as non-toxic by the ACMI in accordance
2
with ASTM D 4236 .
20 pigments have been found comprising both inorganic and organic
substances. Of organic pigments, azo pigments and polycyclic pigments were
found. Only one pigment, copper phthalocyanine, containing a heavy metal
was found. One of the inorganic pigments identified during the survey
contained heavy metals.
All the window colours included in the survey were water-based. The primary
paint binders were acrylates, often thermoplastic (meth)acrylates. Acrylates
consist of acrylic acid and meta acrylic acid and their methyl, ethyl and butyl
esters.
Additives include thickening agents, surfactants, preservatives, anti-foaming
agents and solvents (cosolvents). Preservatives such as isothiazolones and
bronopol are used in window colours. These preservatives are also found in
CE marked products. The window colours also contain a number of glycols
and alcohols.
Chemical analysis
The screening analysis of constituent substances in window colours generally
show that the highest concentrations of extractable substances consist of
alcohols, glycols, ketones, esters and simple hydrocarbons, of which some are
1
ACMI: Art & Creative Materials Institute, Inc.

ASTM D 4236: American standard for the marking of arts and crafts materials for
chronic health hazards.
identified by name and others by substance group. The levels contained in the
various products vary between 2.3 and 5500 mg/kg, equivalent to 0.00023%
to 0.55% in the products. Other substances found in high concentrations in a
single product are unidentified phthalates (two peaks), which upon double
determination were measured at 2700-3100 mg/kg, equivalent to 0.27-0.31%
in the product. Other substances were found in concentrations from approx. 1
mg/kg (0.0001%) and up to approx. 1000 mg/kg (0.1%), mostly at the lower
end. This was also the case with products selected for toxicological assessment
based on the chemical analysis. Thus we are dealing with concentrations
below the general triviality limits stipulated in the Danish EPAs Statutory
Order No. 329 of 16 May 2002 on the classification, packaging, labelling, sale
and storage of chemical substances and products (the Classification Statutory
Order).
Among the metals found were lead, copper, aluminium and titanium. Lead
was detected in two products in concentrations of 12 and 17 mg/kg,
respectively, equivalent to 0.0012 and 0.0017% in the products, and thus
concentration limits are below the 0.15% which triggers requirements for
special labelling of lead-containing products for use as paint or varnish under
the Classification Statutory Order.
Health evaluation
On the basis of the survey and the results of the chemical analysis carried out,
10 substances were selected for toxicological assessment. These are as follows:
Name of substance
CAS no.
Application
Source
1-Naphthol
90-15-3
Intermediary
Data search
Dioxazine
6358-30-1
Pigment
Chemtox
Dimethyloxazolidine
51200-87-4
Preservative
Chemical analysis
Ethylmethyl pyridine
644-98-4
FlavourFlavourF
Chemical analysis
Methyl-benzensulfonamid
5183-78-8
Plasticizer
Chemical analysis
Methenamin
100-97-0
Preservative
(formaldehyde
releaser)
Chemical analysis
Dodecanthiol
112-55-0
Softener
Chemical analysis
2-Ethylhexylacrylat
103-11-7
Paint binder
Data search
Pigment red 146
5280-68-2
Pigment
Chemtox
Pigment yellow 138
30125-47-4
Pigment
Chemtox
Of the 10 substances investigated, three are included on the List of Dangerous

Substances and two substances are on the Danish EPAs guideline list for selfclassification. Literature has been found for these substances that supports
and to some extent adds to the information conveyed by the classification.
Only extremely limited or no data at all has been found that would elucidate
on the toxicological effects of the five other substances. This also applies to
information on possible NOAEL values, which were established/referred to in
only very few of the examined studies.
10
Critical effects originating from the actual use of the surveyed substances were
acute toxic effects (1-naphthol and dimethyloxazolidine) and sensitization
effects (methenamine, docecanethiol and 2-ethylhexylacrylate).
The six substances (dimethyloxazolidine, ethylmethylpyridine,
methylbenzenesulfonamide, methenamine, dodecanthiol and 2ethylhexylacrylate) identified as a result of the chemical analysis carried out
were found in such low concentrations (0.00012 0.097%) that the acute
toxic or irritative properties of the substances may not be expected to
constitute a problem for children using the products.
Those substances that are known to result in hypersensitivity either through
inhalation or skin contact (methenamine, dodecanethiol, 2-ethylhexylacrylate)
may even in small quantities (below the regulatory levels) trigger reactions in
sensitive individuals. However, in the chemical analysis, methenamine, which
causes sensitization both upon inhalation and skin contact, was only found in
concentrations of less than a hundred of the maximum permitted
concentration for use as a preservative in cosmetics. The permitted limit in
cosmetics indicates that the substance is not considered a problem at this
concentration. An epidemiological study among industrial workers has
concluded that there is no risk of respiratory allergies where average
3
concentrations of less than 1 mg/m of methenamine are involved. Given the
concentrations found in the analysis and taking into account the low vapour
pressure, it is unlikely that this concentration could occur during normal use
of the product.
Dodecanethiol and 2-ethylhexylacrylate, which have both been classified as
skin sensitizing are also found in extremely low concentrations in the analysed
products, i.e. <0.047% and 0.018%, respectively.
The literature examined mentioned that dodecanethiol possesses a high
sensitization potential. However, no additional documentation was found to
substantiate this information, nor was information found on the correlation
between exposure and the triggering of an allergic reaction.
Patch tests on humans using solutions of 0.5% 2-ethylhexylacrylate triggered
allergic dermatitis in already sensitized individuals. No information on the
correlation between exposure and primary sensitization was found. The
literature also contains reports on cross-allergy with methylmethacrylate,
which is found in glues and other products.
Thus, neither for dodecanethiol or 2-ethylhexylacrylate has any real
documentation been found for the sensitizing potential of these substances
and consequently the risk children may be exposed to through the use of
window colours containing these substances. If the analysis results are
representative of window colours in general, extremely potent allergens would
have to be involved before substances in such low concentrations could be
considered to constitute a sensitization problem. No data has been found
which would elucidate on the risk for already sensitized persons at the
mentioned concentrations.
On the whole, it may be concluded that documentation has not be found that
would point to the evaluated substances being a risk for children under
conditions of normal use. However, there are always reasons for concern
when children are exposed to sensitizing substances even at low
11
concentrations, especially in the case of children who suffer from e.g. atopical
dermatitis (child eczema) or whose one or both parents have a history of
atopical disorders.
12
1 Introduction
Window colour is a hobby product used by children and adults. The colours
can be applied to smooth and non-porous surfaces, and after drying for
approximately 24 hours the design can be removed and mounted on other
smooth surfaces.
Most window colours on the Danish market are CE marked and are thus
classified for play purposes by children under the age of 14. CE marked
products must conform with the current regulations applying to toys and are
subject to restrictions with regard to the content and emission of certain
substances harmful to health. As not all consumers are familiar with the
marking the Danish EPA assesses that children below the age of 14 will be at
risk of coming into contact with window colours that are not CE marked and
which do not comply with the current regulations for toys.
The CE marking indicates that the toy complies with the safety requirements
of the Danish Consumer Agencys Statutory Order no. 329 of 23 May 1995
on safety requirements for toys and products which by virtue of their outer
appearance might be mistaken for food products. With regard to the toys
chemical properties the regulations require the toy to be manufactured so as
not to constitute a health hazard. This is the responsibility of the toy
manufacturer.
The regulations apply both when the toy:
is used for the intended purpose, and
is used in a way in which children might be expected to use it.
In general, the toy may not contain hazardous substances in quantities that
would constitute a health hazard, i.e. substances that are classified as
hazardous and thus appear on the List of Dangerous Substances or which
conform to the criteria for classification pursuant to Statutory Order no. 329
of the Danish EPA dated 16 May 2002 on the classification, packaging,
labelling, sale and storage of chemical substances and products. Chemical toys
as defined in DS/EN 71-4 on Experimental sets for chemistry experiments
and equivalent activities and DS/EN 71-5 on Chemical toys (sets) other than
experimental sets, respectively may, however, be marketed and sold if the
content of hazardous substances lies below a specified upper concentration
limit provided the chemical substances are necessary for the functioning of the
toy.
According to the assessment of the Danish EPA, CE marked hobby paint
products may contain a maximum of 1% of substances which are harmful,
irritant or corrosive, 1% being the so-called de minimis limit.
Furthermore, the CE marking also signifies that the toy complies with the
requirements concerning the maximum emissions of substances with material
implications for health: these are lead, cadmium, mercury, selenium,
chromium, barium, arsenic and antimony, but the list will be extended to
include other substances in the future. /1/
13
Exposure to substances contained in the products may occur by direct contact

with the stipulated substances on fingers, hands and face, and inhalation.
Consequently, there is a need to chart the substances consumers may be
exposed to through use of window colours.
The products have not been recorded in the product register and it is
therefore necessary to obtain information about constituent substances from
suppliers and producers.
The survey carried out is thus partly based on information obtained from the
literature and available data on the Internet and partly on information
obtained from safety data sheets, suppliers, producers and reviewers of
chemical products. In addition, we have approached the Danish Joint Council
for Creative and Hobby Materials. We obtained an overall list of constituent
substances in window colours handled by Chemtox, a consultant dedicated to
the assessment and evaluation of chemical products with a view to registration
in the product register and the drafting of safety data sheets. For reasons of
confidentiality there is no information on quantities or links to the names of
products and suppliers.
Finally, we visited a number of shops to study the product range and any
information on constituent substances on the packaging.
We purchased ten different window colour products in a variety of colours
with a view to chemical analysis. Subsequently, we selected ten chemical
substances based respectively on the survey and the results of the chemical
analysis and drew up a toxicological profile for these substances.
14
2 Composition of and typical

constituent substances in hobby
paints
Dyes and paints contain four basic ingredients. The chosen basic ingredients
will vary greatly depending on the paints function and appearance and
durability requirements. The four basic components are:
Pigments
Paint binders
Fluid/vehicle
Additives
A brief description of the four types of constituent substance is given below.

2.1
Pigments
Primary pigments give whiteness or colour to the product. Typically, titanium

dioxide, TiO2, is used as white pigment. Coloured pigments produce colour
through the selective absorption of light. Organic pigments (bright/sparkling
colours) and inorganic pigments (earth colours) are used. An example of an
organic pigment is phthalo blue. Inorganic pigments might, for example, be
metal oxides (iron oxide). The actual pigments usually come in powder form,
which are dissolved in a vehicle to obtain the actual colour.
2.2
Paint binders
Paint binders are used to bind pigments and act as an adhesive. There are oilbased or latex-based paint binders. The oil-based ones dry/oxidise upon
exposure to air. Oil-based paint binders may consist of linseed oil or soybean
oil; alkyds may also be used as oil-based paint binders.
Latex-based paint binders are used in water-based paints. The binder is a
solid, plastic-like material. The particles are microscopic in size and are
suspended in the paint. Latex-based paint binders may consist of acrylic or
vinyl acrylic (polyvinyl acetate, PVA), or styrenated acrylics. Polyurethane
polymers may also be used as paint binders.
2.3
Vehicle
Thinners, typically organic solvents, are used for oil-based and alkyd paints,
while water is used for latex-based paints.
15
2.4
Additives
Additives include:
Thickening agents
Surfactants
Preservatives
Anti-foaming agents
Solvents (co-solvents)
Thickening agents are used to obtain the correct paint consistency during use.
Surfactants stabilise the paint to prevent it cutting and provide increased
pigment dispersion. Preservatives prevent undesirable bacteria growth in the
actual paint during storage or once it has been applied. Anti-foaming agents
prevent the formation of foam during mixing and application. Co-solvents are
used with non-water-based paints and are typically organic solvents which
improve dissolution of one or more of the components.
16
3 Survey of manufacturers and

suppliers
Window colours are sold in many shops and the products are normally
supplied by European and American manufacturers. The following section
provides a survey of the market as regards manufacturers, suppliers and
products.
3.1
Manufacturers
European manufacturers dominate the Danish market. Worldwide there are

about 15 hobby colour manufacturers /2/. Most of these manufacturers are
also represented in the Danish market. A list of the manufacturers whose
products are represented in the Danish market is given in Tabel 3.1.
Tabel 3.1 List of window colour manufacturers in the Danish market.
Manufacturer
Country
Internet address
AMOS
Korea
www.amoskorea.com
C Kreul
Germany
www.c-kreul.de/
Frech Verlag
Germany
www.frech.de/
Fun Creativ
Germany
www.funcreativ.de/
Havo
Holland
www.havo-holland.nl/
Lacufa AG, Nerchau Mal- und

Knstlerfarben
Germany
www.nerchau-farben.de
Marabu
Germany
www.marabu-inks.com
Palmer Paint Products
USA
www.toydirectory.com/PalmerPaintProd
ucts/
Pbo Industries
France
www.pebeo.com
Plaid Enterprises
USA
www.plaidonline.com/
Royal Talens
Holland
www.talens.com/
Schjerning Farver A/S
Denmark
www.schjerning-farver.com/
3.2
Suppliers
Window colours are popular and are available in both specialist hobby shops
and in supermarkets. Moreover, window colours are sold directly to
institutions. Certain store chains and shops act as both suppliers and retailers.
Table 3.2 shows a selection of window colour suppliers in Denmark.
Suppliers normally only deal in products from one or two manufacturers.
17
Table 3.2 Selected Danish window paint suppliers.

(-: no Internet address or Internet address not known).
Supplier
Internet address
AV Form A/S
www.avform.dk/
Bogpa A/S
www.bog-ide.dk/
BRIO A/S
www.brio.dk/
Bttzauw ApS
www.bottzauw.dk/
Dica A/S
www.dica.dk/
FDB
www.fdb.dk/
Klitgaard ApS
Panduro Hobby
www.panduro-hobby.dk/
Pbo Color Scandinavia ApS
www.pebeo.dk/
Stenboden A/S
www.stenboden.dk
Terapi-hobby ApS
www.terapi-hobby.dk/
TOP-TOY
www.top-toy.dk/
Vestergaard ApS
3.3
Window colours
Table 3.3 lists the product names of the majority of window colours available
on the Danish market. Any labelling on the product packaging are also listed.
Table 3.3 Window colours on the Danish market and their labelling.
Product name
Marking
Arti'stick
CE
C2 window pen
CE
Crystal Clear window color
CE
Fun & Easy
CE
Fun & Fancy
CE
Funny Window Color
CE
Gallery Glass Window Color
AP Non Toxic
Glass Deco
none
Mak'easy window color
CE
SunArt stain
CE
Vinduesmaling
CE
Window Art
CE
In addition to these, there are a number of outline paints for drawing outlines.
These paints are normally black or white.
18
4 Survey of constituent substances

in window colours
The survey of constituents substances is based on information obtained from
manufacturers, suppliers and other relevant sources. As point of departure we
set out to obtain available information in the form of safety data sheets and
other product information from suppliers and manufacturers. Moreover, we
have made every effort possible to obtain additional information from the
manufacturers subsequent to agreement with the suppliers. All manufacturers
have at least been contacted by post, either directly or through the Danish
supplier. When applying to these manufacturers we have included an
accompanying letter from the Danish EPA containing information about the
project and reference to the responsible person at the Danish EPA. We
followed up our requests for information both by telephone and post. We
received information in the form of safety data sheets on seven of the ten
products, which were adopted for chemical analysis. In addition, we received
safety data sheets and supplementary information on constituent ingredients
in window colours from one other supplier.
However, the survey was not of a scope that would allow the undertaking of
an extremely comprehensive data collection process. Therefore, to
supplement information a list of constituent substances in window colours
was obtained from the consultancy firm, Chemtox. The list contains all the
constituent substances in window colour products handled by Chemtox with
the purpose of evaluation whether registration in the Product Register and the
drafting of a safety datasheet was necessary.
Thus the survey is based on the window colour safety data sheets, additional
information obtained directly from suppliers and manufacturers and the
above-mentioned overall list. The safety data sheets must at least contain
information on hazardous substances as defined in Statutory Order no. 559
off the Danish Working Environment Authority dated 4 July 2002 on special
obligations imposed on manufacturers, suppliers and importers, etc. of
substances and materials comprised under the Work Environment Act. In
certain cases the data sheets also provide information on other substances in
the product. The survey included data sheets and other information from a
total of eight suppliers. Furthermore, the results of the survey have been
presented to the Danish Joint Council for Creative and Hobby Materials. The
Joint Council has confirmed that there is agreement between the Councils
information and the results of the survey. The data collected from the
suppliers taken together with the list from Chemtox may thus be assumed to
present an acceptable picture of the constituent substances in the majority of
window colours on the Danish market. Naturally there may be other products
which are imported directly to specialist shops, etc. where assessment of the
constituent substances has not been may pursuant to current legislation.
In the following lists constituent substances have been classified according to
the four basic components.
Pigments
19
4.1
Paint binders
Fluid/vehicle
Additives
Pigments
Several of the pigments used are used in other types of paint and also in other
types of products used in the dying of e.g. textiles. Table 4.1 shows that both
inorganic and organic pigments are used in window colours.
Of organic pigments, azo pigments and polycyclic pigments were found. Only
one pigment, copper phthalocyanine, containing a heavy metal was found.
None of the other inorganic pigments identified contain heavy metals.
20
Table 4.1 Pigments in window colours and their physico-chemical properties (data
from 11, 14 and 22). - indicates that value is not available, nr, that it is not relevant.
Carbon black (C)
Trivial name /
synonym
Pigment black 7
1333-86-4
C.I.
number
77266
Conc.
(%)
0-2
Use in
cosmetics 1)
1
Diarylids (C32H26Cl2N6O4)
Diazopyrazolone
(C32H24Cl2N8O2)
Pigment yellow 12
6358-85-6
21090
0-2
Pigment orange 13
3520-72-7
21110
Dioxazine (C34H22Cl2N4O2)
Pigment violet 23
6358-30-1
Copper phthalocyanine
(C32H16CuN8)
Pigment blue 15
Mica
Pigment white 20
and 26
Name of substance (formula)
CAS no.
MW
S (g/L)
LogKow
12.0
insoluble
in
No
629.5
<1
5-7
0-2
No
623.5
51319
0-2
147-14-8
74160
576.0
<1
6,6
12001-26-2
77019
No
in
Iron(II)oxide (FeO)
Iron oxide
1345-25-1
77489
71.8
in
Iron(III)oxide (Fe2O3)
Pigment red 101
1309-37-1
77491
0-2
159.7
insoluble
in
Phthalocyanine (C32H18N8)
Pigment blue 16
574-93-6
74100
0-2
512.5
<1
(Mono-chlorinated copper
Pigment blue 15:1
phthalocyanine (C32H15ClCuN8)
12239-87-1
74250
No
Phthalocyanine green
<1
1328-53-6
74260
4,4'- (3,3'-dichloro 1,1'-biphenyl

-4,4'-diyl)bis(azo) bis 2,4dihydro-5-methyl-2-(4Pigment orange 34
methylphenyl)- 3H-pyrazol-3one
Pigment green 7
15793-73-4
21115
No
N-(4-chloro-2,5dimethoxyphenyl)-3-hydroxy-4[[2-methoxy-5Pigment red 146

[(phenylamino)carbonyl]phenyl
]azo]naphthalene-2carboxamide (C33H27ClN4O6)
5280-68-2
12485
No
N-(5-chloro-2-methylphenyl)-3hydroxy-4-[[2-methoxy-5[(phenylamino)carbonyl]phenyl Pigment red 147

]azo]naphthalene-2carboxamide (C32H25ClN4O4)
68227-78-1
No
2,2'-[(2,2',5,5'-tetrachloro-[1,1'biphenyl]-4,4'-diyl)-bis(azo)]
bis-N-(2,4-dimethylphenyl)-3oxo-butanamide
(C36H32Cl4N6O4)
Pigment yellow 81
22094-93-5
No
2,2'-[(3,3'-dichloro[1,1'biphenyl]-4,4'diyl)bis(azo)]bis[N-(4-chloro2,5-dimethoxyphenyl)-3oxobutyramide]
(C36H32Cl4N6O8)
Pigment yellow 83
5567-15-7
21108
818.5
3,4,5,6-tetrachloro-N-[2(4,5,6,7-tetrachloro-2,3-dihydro1,3-dioxo-1H-inden-2-yl)-8Pigment yellow 138

quinolyl]phthalimide
(C26H6Cl8O8)
30125-47-4
56300
No.
Quinacridone (C20H12N2O2)
Pigment violet 19
1047-16-1
73900
0-2
312.3
insoluble
Titandioxide (TiO2)
Pigment white 6
13463-67-7
77891
0-2
1
79.9
insoluble
in
1) The figures in this column indicate how the pigments may be used in cosmetics products: 1:
Pigment permitted in all cosmetics products; 2: Pigment permitted in all cosmetics products
with the exception of cosmetics products for use around the eyes, i.e. eye makeup and
associated cleansing products; 4: Pigment only permitted in cosmetics products which are only
intended to be in short-term contact with the skin. No: May not be used.
21
None of the pigments appear on the List of Dangerous Substances or the

Danish EPAs guideline list for self-classification of substances. Azo pigments
are easily broken down enzymatically, releasing aromatic amines among other
substances. Several of these aromatic amines are suspected of having
carcinogenic effects.
As Table 4.1 shows, nine of the listed pigments are not included on the list of
pigments that are permitted for use in cosmetics products. The Danish EPA
assesses that the pigments which under cosmetics regulations may only be
used in short-term contact with the skin ought not normally be used in
products for children.
4.2
Paint binders
Acrylates and polyurethane polymers are used as paint binders in window

colours. Acrylates and methacrylates are widely used as paint binders both in
water soluble paints and solvent-based paints. Poly(meth)acrylates represent a
major group of substances whose composition can be varied depending on the
desired properties /3/. Thermoplastic (meth)acrylates are often used as paint
binders. Acrylates consist of acrylic acid and meta acrylic acid and their
methyl, ethyl and butyl esters /4/.
Table 4.2 shows which paint binders and residual monomers may be found in
window colours according to the survey. In addition, the table shows the
hazard classes in which the products are placed and their classification on the
List of Dangerous Substances.
Name of substance
(formula)
Acrylic acid (C3H4O2)
Table 4.2 Paint Binders and residual monomers in window colours and their physicochemical properties (data from 11, 14 and 23) and classification. (28). - indicates that
value is unknown.
Percentage
Classification
CAS no.
MW
S (g/L)
LogKow
Hazard classes
content (%)
Flammable,
R10 Xn;R21/22 C;R35
Harmful to health,
N;R50
79-10-7
72.1
> 100
0.35
Corrosive,
Dangerous to the
environment
Highly flammable,
Harmful to health,
Local irritant,
Sensitizing
F;R11 Xn;R20/21/22
Xi;R36/37/38 R43
Ethylacrylate (C5H8O2)
140-88-5
100.1
15
1.32
Ethylacrylate-methacrylic
acid polymer
25212-88-8
2-Ethylhexylacrylate
(C11H20O2)
103-11-7
184.3
<1
4.09
Local irritant,
sensitizing
Xi;R37/38 R43
Methylmethacrylate
(C5H8O2)
80-62-6
100.1
15
1.38
Highly flammable,
Local irritant,
Sensitizing
F;R11 Xi;R36/37/38
R43
Polyurethanepolymer
68400-67-9
Vinylacetat (C4H6O2)
108-05-4
86.1
20
0.73
MW= Molecular Weight; S = Solubility in water;
22
No
No
Highly flammable
F;R11
4.3
Medium
All the window colours encountered were water-based, i.e. their medium is
water. In addition, the products may contain small amounts of solvent.
4.4
Additives
According to the information gathered, window colours contain a number of

additives.
Table 4.3 shows a list of the additives used in window colours, selected
physico-chemical properties and the hazard classes in which the substances
are placed and the classification of substances from the List of Dangerous
Substances.
23
Table 4.3 Additives in window colours and their physico-chemical properties (data from 11, 14 and 23), and
their classification (28, 33). - indicates that value is unknown.
Name of substance
Percentage
Hazard classes
Classification 1)
CAS no.
MW
S (g/L)
LogKow
(formula)
content (%)
2-Amino-2-methylpropanol
124-68-5
89.1
1000
-0.74
Local irritant
Xi; 36/38 R52-53
(C4H11NO)
Ammonia (H5NO)
1336-21-6
35.0
1000
-2.66
Corrosive,
Dangerous to the
environment
C; R34 N; 50
2-(2-(2butoxyethoxy)ethoxy)ethanol
143-22-6
Butyl diglycoletheracetate
(C10H20O4)
124-17-4
204.3
31
1.3
Dangerous to the
environment
R52/53
<0.0012
26172-55-4
149.6
Sensitizing
R43
Diisopropyleneglycole
(C6H14O3)
110-98-5
134.2
Dipropyleneglycol (C6H14O3)
25265-71-8
134.2
> 100
-1.07
Dipropyleneglycolmethylethe
r (C7H16O3)
34590-94-8
148.2
1000
-0.35
Ethanol (C2H6O)
64-17-5
46.1
> 100
-0.31
Highly flammable
F;R11
Ethylenglycol (C2H6O2)
107-21-1
62.1
> 100
-1.36
Harmful to health
Xn;R22
Formaldehyde (CH2O)
50-00-0
30.0
400
0.35
Carcinogenic, toxic,
corrosive,
sensitizing
Carc3;R40
T;R23/24/25
C;R34 R43
<0.0004
2682-20-4
115.1
Sensitizing
R43
Harmful to health,
Local irritant,
Dangerous to the
environment
Xn;R21/22
Xi;R37/38-41
N;R50-53
5-Chlor-2-methyl-4-isothiazol3-one (C4H4ClNO)
2-Methyl-4-isothiazol-3-one
(C4H5NOS)
2-Bromo-2-nitropropane-1,3diol (C3H6BrNO4)
Naphthol (C10H8O)
52-51-7
200.0
>100
-0.64
0-2
1321-67-1
144.2
2.7
Harmful to health,
local irritant
Xn;R21/22
Xi;R37/38-41
1-Naphthol (C10H8O)
90-15-3
144.2
0,866
2,2-Oxydiethanol (C4H10O3)
111-46-6
106.1
> 100
-1.47
Polypropylener glycol
25322-69-4
1-5
57-55-6
76.1
> 100
-0.92
Triethanolamine (C6H15NO3)
102-71-6
149.2
> 100
-1.0
Sensitizing
R43
Triethylene glycol (C6H14O4)
112-27-6
150.2
>100
-1.98
Propylene glycol (C3H8O2)
1) Classification from the List of Dangerous Substances or from the guideline list for selfclassification (in italics).
During the survey information was found on naphthol with Cas no. 1321-671. As no essential data was found for the stated Cas no. (1321-67-1), which is
a mixture of isomers, the data specified below is for 1-naphthol with Cas. no.
90-15-3.
The two isothiazolinones 5-chloro-2-methyl-4-isothiazol-3-one (Cas no.
26172-55-4) and 2-methyl-4-isothiazol-3-one (Cas no. 2682-20-4), which in
a 3:1 mixture are marketed under the trade name of Kathon, occur commonly
in window paints. The same applies to 2-bromo-2-nitropropane-1,3-diol
(bronopol) and formaldehyde, which presumably most commonly stem from
impurities in the constituent raw materials or from releases from
formaldehyde-releasers. Isothiazolonone and bronopol are also encountered in
CE marked products.
24
The two isothiazolinone derivatives are both contained by window colours in

low concentrations which lie below the de minimis limit according to the
safety data sheets for the investigated products.The substances also occur e.g.
in cosmetics products, where the permitted limit is 0.0015%.
25
26
5 Chemical analysis
5.1
Test products
The window colours were analysed for their content of chemical substances.
Table 5.1 lists the products' colours.
Table 5.1 test products selected for qualitative analysis.
V-No.
Colour
V1
White
V2
Glitter green
V3
Ultramarine
V4
Blue
V5
Dark Blue
V6
V9
Oriental Blue
Mixed:
Cobalt Blue
Sunny Yellow
Violet
Mixed:
Puppy Red
Liner Black
Royal Green
Lemon yellow
V10
Bright Red
V7
V8
5.2
Methods of analysis

Approx. 5 g of the product was taken and extracted with dichloromethane
added internal standards by Soxhlet extraction for 16 hours. A part sample of
the extract was removed and analysed directly and concentrated by combined
gas chromatography and mass spectrometry (GC/MS) by scanning over a
larger mass area. The contents were analysed compared to relevant external
standards (indicated with an * in the Analysis Results) or internal standards
(other extractable substances). Quantification of the components calculated
compared to internal standards is semi-quantitative, thus implying greater
uncertainty (estimated 50-200%). In the case of quantification compared to
external standards uncertainty was estimated at 10-20%
The analysis were carried out as true double determinations. The detection
limit was 1-5 mg/kg for the components that are semi-quantified and 1 mg/kg
for the components where external standards were included.
5.2.2 X-ray analysis (elements)
A part sample was subject to X-ray analysis for the content of 40 elements.
This analysis was outsourced.
27
The analysis were carried out as true double determinations. The detection
limit was 10 mg/kg. Analysis uncertainty was 5-10% RSD.
5.2.3 Water content using Karl Fisher titration
The water content of the sample was determined by automatic titration with
the help of Karl Fisher (KF) titration.
The analysis were carried out as true double determinations. Analysis
uncertainty was 10% RSD.
5.2.4 IR screening
A part sample was removed from the sample which was pressed into a
potassium bromide tablet and subject to FT-IR analysis to determine the main
organic contents of the sample by comparison with data library spectra.
The analysis were carried out as true double determinations. This analysis will
not be reported on separately. The results of the screening were used to
underpin the results of the GC/MS screening.
5.3
Analysis results

Table 5.2 and Table 5.3 shows the results of the GC/MS screening. The two
results refer to double determinations. All identification of substances was
made based on the mass spectrum through comparison with mass spectra in
the data library. The spectra giving the closest match were assessed using
scientific judgement in each case. Where identification is not possible the
components are designated by group as a total amount or specified with a
substance name in parentheses, this name being the most viable estimate of
what the substance might be. The detection limit was 1-5 mg/kg.
In conformity with the wishes of the Danish EPA, standards have been
selected based on the results of the survey of individual components. These
components have therefore been calculated against the standards. Semiquantitative calculations against internal standards were made for all other
organic components. The components calculated against external standards
are indicated with * in the table. The detection limit for components
calculated against external standards is 1 mg/kg.
For certain components the content was so great that it was necessary to
dilute the sample in order to calculate the content correctly. These
components are marked with an ^ in the table.
28
Table 5.2 Results of analysis for extractable substances in V1-V5. The two results refer
to the double determinations. Results are given in mg/kg. The detection limit is stated
above.
V1
V2
Dimethyloxazolidine
74
43
48
Butylether
(Hexylen glycol)
2,2-oxydiethanol*
Hexanol
36
53
Ethylhexanol
170
138
Acetophenone
Chloromethylisothiazolone
5.4
11
7.9
6.5
Benzoisothiazolone
Chloraniline
Chloroisocyanatobenzene
Caprolactam*
2.0
7.3
Chloro-nitro-benzenamine
(Chloro-benzotriazol)
Napthalenol*
Naphthalene
Nitrotriazaadamantan
8.3
9.5
Ethylhexylacrylat*
3.2
8.7
180
150
87
N-propyl-2-hydroxy-14.3
oxohexahydro-1H-azepin
Chloralkanes (two peaks)
Ethylmethyl pyridine*
(sum of two peaks)*
Methyl piperazine
Nonylphenol*
(2,2-dimethyl-1-(2-hydroxy1-methylethyl)propyl
propansyre ester)
(2-methyl-propansyre 2ethyl-3-hydroxyhexylester)
(Methenamine)
Hydroxy biphenyl
Unidentified phthalates
3100
(sum of two peaks)
(Dibutylphthalate)
37
DEHP
37
Benzophenone
4.3
Dodecanthiol*
Dodecylmethyl sulfid
Thiabendazole
Bis(ethylhexyl)maleat
Alkennitrile
Unidentified alkanes,
240
360
130
100
1500
alkenes, alkoholes,
cycloalkanes/- alkenes
Unidentified carboxylic
72
120
140
110
85
acids, esters, ketones,
aldehydes and amides
Unidentified glycoles and
190
330
1600
1500
365
oxycompounds
Unidentified aromatic
19
compounds
Other unidentified
28
26
980
820
220
-: lower than detection limit
( ): identification not possible; name of substance the most viable estimate
*: quantified against external standards
^: quantified using diluted sample
V3
V4
V5
29
46
3.8
51
1200
39
58
-
59
1300
37
63
-
75
15
-
54
7.6
-
990
960
1300
1300
2700
35
17
3.1
1500
450
88
120
280
13
560
470
92
110
300
13
590
7.9
7.6
370
2.9
7.8
240
72
220
220
180
110
328
32
56
1200
1100
14
180
250
170
3100
3300
200
190
29
Table 5.3. Results of analysis for extractable substances in V6-V10 The two results refer
to the double determinations. Results are given in mg/kg. The detection limit is stated
above.
V6
V7
Dimethyloxazolidine
Butylether
(Hexylen glycol)
2,2-oxydiethanol*
Hexanol
Ethylhexanol
71
70
Acetophenone
Chloromethylisothiazolone 8.8
Benzoisothiazolone
Chloraniline
Chloroisocyanatobenzene
Caprolactam*
27
22
Chloro-nitro-benzenamine
(Chloro-benzotriazol)
Napthalenol*
Naphthalene
Nitrotriazaadamantane
Ethylhexylacrylate*
8.9
10
4.9
3.8
2.6
N-propyl-2-hydroxy-1oxohexahydro-1H-azepine
Chloralkanes (two peaks)
Ethylmethyl pyridine*
58
59
(sum of two peaks)*
Methyl piperazine
32
30
Nonylphenol*
51
54
81
(2,2-dimethyl-1-(2-hydroxy- 1-methylethyl)propyl
propansyre ester)
(2-methyl-propansyre 2ethyl-3-hydroxyhexylester)
(Methenamine)
Hydroxybiphenyl
Unidentified phthalates
(sum of two peaks)
(Dibutylphthalate)
DEHP
Benzophenone
3.0
3.7
2.4
2.3
2.5
Dodecanthiol*
Dodecylmethyl sulfid
Thiabendazol
Bis(ethylhexyl)maleat
Alkennitrile
Unidentified alkanes,
900
910
27
26
62
alkenes, alkoholes,
cycloalkanes/- alkenes
Unidentified
280
400
44
39
58
carboxylicacids, esters,
ketones, aldehydes and
amides
Unidentified glycoles and
760
840
730
oxycompounds
Unidentified aromatic
1.5
compounds
Other unidentified
170
180
68
68
49
( ): identification not possible; name of substance the most viable estimate
*: quantified against external standards
^: quantified using diluted sample
30
VC8
V9
V10
14
3.1
-
12
11
21
11
4.9
78
41
3.2
5.2
-
5200
5.1
11
1.4
-
5500
5.1
5.7
1.3
-
3.6
78
40
3.8
5.2
-
260
-
270
-
970^
850^
95
-
3500^
3000^
4800^
4100^
3.6
-
4.5
-
13
1.2
2.8
62
390
380
27
26
60
140
150
63
57
630
2.5
6.2
1200
1200
1.8
3.6
4.2
23
18
72
210
230
15
18
5.3.1.1 X-ray analysis

Table 5.4 shows the results of the X-ray analysis. The elements not listed in
the table were not detected by the analysis. Only single determination analysis
were made due to the precision of the analysis. The detection limit is 10
mg/kg.
Table 5.4. Results of X-ray analysis. Results are given in mg/kg.
V1
V2
V3
V4
V5
V6
Sodium
480
-*
910
Aluminium
77
Silicon
520
740
130
Phosphorus
130
Sulphur
880
490
1100
Chlorine
32
Potassium
Calcium
12
21
Titanium
5100
Copper
18
65
Lead
Bromine
320
150
( ): detection limit increased to 50 mg/kg
740
400
2700
100
360
20
260
540
750
330
1000
41000
400
17
33
12
24
870
150
880
250
19
28
-
V7
V8
V9
V10
440
22
440
-
530
81
470
-
2000
320
170
1700
350
39
18
17
-
660
18
36
2700
92
-
5.3.1.2 Water content

The tables below show the results of the analysis for water content. The two
results refer to the double determinations.
Tabel 5.5 Results of water analysis of V1-V5. Results are given in %.
V1
V2
V3
V4
Water
44
46
47
48
46
46
64
V5
67
62
Tabel 5.6 Results of water analysis of V6-V10. Results are given in %.

V6
V7
V8
V9
Water
49
5.4
48
46
45
42
41
49
60
V10
51
49
52
Summary of analysis
The screening analysis of constituent substances in window paints generally

show that the highest concentrations of extractable substances consist of
alcohols, glycols, ketones, esters and simple hydrocarbons; of these, some are
identified by name and others by substance group. The levels contained in the
various products vary between 2.3 and 5500 mg/kg, equivalent to 0.00023%
to 0.55% in the products. Other substances found in high concentrations in a
single product are unidentified phthalates (two peaks), which upon double
determination were measured at 2700-3100 mg/kg, equivalent to 0.27-0.31%
in the product.
Other substances were found in concentrations from approx. 1 mg/kg
(0.0001%) and up to approx. 1000 mg/kg (0.1%), mostly at the lower end.
This was also the case with products selected for toxicological assessment
based on the chemical analysis. The substances concerned are those shown in
Table 5.7.
31
Table 5.7 Substances selected for toxicological assessment.

Name of substance
Measured concentration in
mg/kg
Dimethyloxazolidine
12-75
58-59
Methylbenzensulfonamid
850-970
Methenamine
1.2-13
Dodecanthiol
2.9-470
% in the product
0.0012 - 0.0075
0.0058 - 0.0059
0.085 - 0.097
0.00012 - 0.0013
0.00029 - 0.047
Among the metals found were lead, copper, aluminium and titanium. Lead
was detected in two products in concentrations of 12 and 17 mg/kg,
respectively, equivalent to 0.0012 and 0.0017% in the products. During the
survey information was found about one of the products. This information
does not indicate that the product contains lead-containing pigments and an
impurity might be involved. In the case of the other product, neither supplier
nor manufacturer submitted any information. However, the concentration
limits found were below the 0.15% which triggers requirements for special
marking of lead-containing products for use as paint or varnish under
Statutory Order no. 329 of the Danish EPA dated 16 May 2002 on the
classification, marking, sale and storage of chemical substances and products.
Thus the analysis determined approx. 50% of the products' contents.
Other constituent substances will primarily consist of paint binders such as
acrylic resins and fillers.
32
6 Selected substances and data

searching
6.1
Basis for the selection of substances
During the initial survey, 20 substances were identified in the pigment group,
7 in the paint binder and their residual monomers group and 18 substances
were identified in the additive group. Among these substances, which were
identified based on general information about the constituent substances
contained in window colours and specific information on the test products,
only 4 were re-encountered in connection with the chemical analysis. In this
connection, we must stress that the screening analysis do not identify all
substances individually. A number of substances are grouped by their group
names alkanes, alkenes, alcohols, cycloalkanes/cycloalkenes, glycols and
oxygen compounds, aromatic compounds and other unidentified substances.
Many of the substances which were found during the survey must therefore
be assumed to be included under these group names. This most certainly
applies to the additives identified during the survey and shown in Table 4.3.
The survey also covers a relatively large number of pigments, which one
would not expect to find through a screening analysis of just 10 products.
Based partly on the results of the survey and partly on the chemical analysis of
the test products, the Danish EPA has selected ten substances for assessment
of their health implications. A toxicological profile based on the immediately
accessible literature was drawn up for these substances.
In making the selection, account was taken of the concentration of the
substances and any already existing knowledge on/or assessments of the
substances in connection with consumer products. Thus, the selected
products represent those products found in the highest concentrations in the
test products and those substances about which the Danish EPA wishes
further information.
6.2
The selected substances
Tabel 6.1 lists the substances selected with a view to assessment of their
implications for health. The table also shows whether the substances were
identified by chemical analysis or based on information from suppliers, and
the concentrations of the substances. Finally, the table lists the substances'
presumed application in the products.
33
Tabel 6.1 Review of substances selected for assessment of their health implications.
Name of substance
CAS no.
Conc. (%)
1-naphthol
90-15-3
Dioxazine
6358-30-1
0-2
Dimethyloxazolidine
51200-87-4
0.0012-0.0075
644-98-4
Methyl-benzenesulfonamide 5183-78-8
Application
Source
Intermediate product
of pigment
production
Data search
Pigment
Chemtox
Preservative
Chemical analysis
0.058-0.059
Flavour
Chemical analysis
0.085-0.097
Softener
Chemical analysis
Methenamine
100-97-0
0.00012-0.0013
Preservative
(formaldehyde
releaser)
Chemical analysis
Dodecanthiol
112-55-0
0.00029-0.047
Plasticizer
Chemical analysis
2-ethylhexylacrylate
103-11-7
0.0013-0.018
Paint binders
Chemical analysis
Pigment red 146
5280-68-2
Pigment
Chemtox
Pigment yellow 138
30125-47-4
Pigment
Chemtox
6.3
Data search
Data on the physico-chemical properties and the health implications were

obtained from a number of Internet-based databases and reference works.
1. Chembank
2. Chemfinder
3. Ullmann
4. ECB
5. SAX
6. TOXLINE
7. MEDLINE
8. HSDB
9. IRIS
10. CCRIS
11. GENETOX
12. IUCLID
13. PHYSPROP
14. Web of Science
15. NTP
There will be some overlapping between several of these databases. Table 6.2
reviews the results of the data search. The list shows whether the 14 databases
contain data on the individual substances.
In addition, we examined whether the substances appeared on the chemical
lists of the Danish EPA, the annex to the Cosmetics Statutory Order or on the
positive list of the Danish Veterinary and Food Administration (list of food
additives).
34
Table 6.2. Review of data search results. The database and data source numbers refer
to the following: 1. Chembank, 2. Chemfinder, 3. Ullmann, 4. ECB, 5. SAX, 6. TOXLINE, 7.
MEDLINE, 8. HSDB, 9. IRIS, 10. CCRIS, 11. GENETOX, 12. IUCLID, 13. PHYSPROP, 14. Web of
Science, 15. NTP. + indicates data found. - indicates no data found.
Substance
CAS no.
10 11 12 13
14
15
1-Naphthol
90-15-3
Dioxazine
6358-30-1
Dimethyloxazolidine
51200-87-4
644-98-4
Methylbenzenesulfonamide
5183-78-8
Methenamine
100-97-0
Dodecanthiol
112-55-0
103-11-7
Pigment red 146
5280-68-2
Pigment yellow 138
30125-47-4
The table shows that there is only limited data available in the literature
examined on several of the substances, and in the case of some substances,
only physico-chemical data. Such is the case with ethylmethyl pyridine (CAS
no. 644-98-4), methylbenzenesulfonamide (CAS no. 5183-78-8) and the two
pigments, as shown by Table 6.2.
Data on the individual CAS nos. is divided according to the various
toxicological properties as illustrated in Tabel 6.3. The table only shows a (+)
or (-) if data was found on the mentioned properties, thus the table says
nothing about the actual effects of the substances or about the quality of data.
Secondary sources have been used in the main, as a result of which the quality
of data varies greatly. In by far the majority of cases results have only been
included from the sources referred to where the test conditions are reasonably
well described.
35
Tabel 6.3 Identified human toxicological data divided by CAS nos. identified.
Allergy and hypersensitivity
Organ damage
Cancer
Damage to the
reproductive process
and the foetus
CAS No.
1-Naphthol
90-15-3
Dioxazine
6358-30-1
Dimethyloxazolidine
51200-87-4
644-98-4
5183-78-8
Methenamine
100-97-0
Dodecanthiol
112-55-0
103-11-7
Pigment red 146
5280-68-2
Pigment yellow 138
30125-47-4
36
Genetic damage
Skin contact
Material
Irritation and
corrosiveness
Ingestion
Subacute/chronic toxicity
Inhalation
Acute toxicity
7 Toxicological profile of selected

substances
7.1
Toxicological profile of 1-naphthol

7.1.1.1
Identification
Chemical name
EINECS name
CAS no.
Molecular
formula
1-naphthol
1-naphthol
90-15-3
C10H8O
OH
Structural
formula
Applications
1-Naphthol is used in the manufacture of paints and colours (e.g. diazo
pigments), of synthetic perfumes and of hair dyes. The substance is also used
in the production of the insecticide Sevin (carbaryl) and anti-oxidants /12/.
Synonyms
The following synonyms have been found for 1-naphthol /12/:
alpha-naphthol
C.I. 76605
durafur developer D
fouramine ern
fourrine 99
fourrine ern
furro ER
1-hydroxynaphthalene
nako TRB
1-naphthalenol
oxidation base 33
37
Regulation
EU/DK classification
Xn; R21/22 Xi; R37/38-41
The Danish EPAs guideline list for self- not assessed
classification
The Cosmetics Statutory Order
highest permitted concentration in hair
dye is 2.0%
Foodstuffs (the positive list)
not on the positive list
Foodstuffs (the flavour list, 2002)
not on the flavour list 2002
not on the OEL list
The Danish Working Environment
Authority's occupational exposure limit
list
7.1.1.2
Physical/chemical properties
Table 7.1. Physico-chemical properties of 1-naphthol.

Reference
solid
Physical form
substance
Molecular weight (g/mol)
144.17
22
Melting point (C)
95
22
Boiling point (C)
288
22
Vapour pressure (Pa)
0.03653
22
Specific weight (kg/L)
1.22
14
Log Kow
2.85
22
Water-solubility (mg/L)
866
22

Absorption
Tests involving the application of 1-naphthol to human skin indicated approx.
50% was absorbed percutaneously /8/.
Metabolism
An old study (1950) shows that 1-naphthol is primarily excreted in the urine
following subcutaneous administration. Most of the substance is excreted
within three days /16/. Within 35 minutes of application to the skin, the
highest organ concentrations were found in the lungs, thyroid gland, heart,
adrenal glands, spleen, thymus and brain. Following oral ingestion the highest
concentrations were found in the kidneys, blood plasma, skin, liver and
thyroid gland /16/.
7.1.2.1 Acute toxicity
Inhalation
3
The LC50 for rats is recorded as > 420 mg/m /hour /8/.
Ingestion
The LD50 for oral ingestion in rats is recorded as 1,870 mg/kg body weight
/6/.
The presumed lethal dose is recorded as 50-500 mg/kg /8/.
The substance is classified as Harmful with R phrase R22, Harmful if
swallowed, on the List of Dangerous Substances.
38
Skin contact
The LD50 value for rabbits in the literature examined was recorded as being
880 to 990 mg/kg body weight /8,12/.
The substance is classified as Harmful to Health with R-phrase R21, Harmful
in contact with skin, on the List of Dangerous Substances.
Irritation and corrosion
The substance can cause irritation to the respiratory organs /10/.
The substance may cause irritation in contact with the skin and eyes /8,10/.
An animal test a concentration of 2.5% did not result in irritation of rabbit
skin. The substance resulted in minimal eye irritation at concentrations of up
to 1.5%, but was irritating to rabbits eyes at 2 and 2.5% /16/. No tests using
higher concentrations were found, but the substance is classified in its pure
form as constituting a risk for serious eye damage.
1-naphthol is classified as irritant with R-phrases R37/38, Irritating to
respiratory system and skin and with R41 and risk of serious damage to eyes,
on the List of Dangerous Substances.
7.1.2.2
Allergy and hyper-sensitivity

No relevant data was found in the literature examined.
Organ damage
Genetic damage
Both negative and positive results have been found in Ames tests on different
strains of Salmonella Typhimurium. The results of chromosome aberration
tests in the eukaryotic fungus, Neurospora Crassa, were negative, whereas
chromosome aberration tests on the root cells of the plant Allium Cepa
produced positive results /20,21/. Unscheduled DNA synthesis (UDS), which
is a test to show repair of primary DNA damage produced negative results in
rat liver cells. Negative results were also found in gene mutation assays of
mouse lymphoma cells and in two in vivo chromosome aberration tests.
Positive results were found in DNA repair tests in a single E. coli strain
(JC5547). The substance is not considered to be a mutagen /16/.
Cancer
Damage to the reproductive process and the foetus
A solution of 1-naphthol (0.5 %, 1:1 med hydrogen peroxide) applied to
shaved rat skin (2 mg/kg/day) on days 1, 4, 7, 10, 13, 16 and 19 of the
gestation period did not show teratogenic effects or other toxic effects on the
foetus/16/. Oral administration of 1-naphthol in concentrations up to 80
mg/kg on days 6-15 of the gestation period did not result in treatment related
effects on either the progeny or the mother animals /16/.
1-naphthol is designated as an experimental teratogen and is attributed
reproduction-toxic effects by a single source /12/. However, no details
39
concerning test results are given and no further data has been found in
support of this evaluation.
7.1.3 Conclusion
1-naphthol can be absorbed through the skin. The substance is classified as
Harmful with R-phrases R21/22, Harmful in contact with skin and if
swallowed, and as an irritant with R-phases R37/38, Irritating to Respiratory
system and skin, and R41, risk of serious damage to eyes.
In the literature we found positive mutagenicity data relative to the Ames' test
and chromosome aberration test on plant cells. Negative Ames' tests were also
reported as was one negative chromosome aberration test on a eukaryotic
fungus. No immediate conclusions can be drawn on the basis of this data.
We found no studies showing carcinogenic properties. Rat experiments
involving skin contact and oral administration of 1-naphthol shows no effects
on foetuses or foetal development. However, one single source described the
substance as having reproduction-toxic effects, but gives no further details.
7.2
Toxicological profile of dioxazine

7.2.1.1
Identification
Chemical name
EINECS name
CAS no.
Molecular
formula
dioxazine
8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo[3,2b:3',2'-m]tripheno dioxazine
6358-30-1
C34H22Cl2N4O2
Cl
O
Structural
formula
N
Et
Et
N
N
Cl
Application
Dioxazine is used as a colorant in products such as paint and artists paints.
Synonyms
The following synonyms are used for dioxazine (5):
diindolo[3,2-b:3',2'-m]triphenodioxazine
8,18-dichloro-5,15-diethyl-5,15-dihydro C.I. Pigment Violet 23
C.I. 51319
40
Regulation
not classified
The Danish EPAs guideline list for self- not assessed
classification
permitted in cosmetics products
which are only intended to be in
short-term contact with the skin
not on the OEL list
Authority occupational exposure limit
list
7.2.1.2 Physical/chemical properties
Tabel 7.2 summarises the physico-chemical properties of dioxazine.
Dioxazine is a solid substance at room temperature and due to the extremely
high melting point, vapour pressure is assessed as being very low at room
temperature. No data was found on the partition coefficient and boiling point
of the substance.
Tabel 7.2 Physico-chemical properties of dioxazine.
-no data was found *based on assessment.
Source
Physical form
solid substance
14
588
14
Melting point (C)
430 - 455
14
Boiling point (C)
very low *
14
1.4 to 1.6
14
Log Kow
very low*
14

Inhalation
Ingestion
In rodents the substance has displayed low acute toxicity upon ingestion /5/.
Skin contact
In rodents the substance has displayed low acute toxicity upon skin contact
/5/.
Tests on rabbits have shown dioxazine to be an eye irritant but not a skin
irritant /5/.
41
7.2.2.2 Subacute/chronic toxicity

Limited studies on rats given repeated oral doses of the substance showed no
toxic effects. There is no information on the doses used in the studies /5/.
In studies on the mutagenicity of selected azo dyes, the substance tested
negative in Ames' tests /6/.
The substance is also on the US EPA's list of inert substances in pesticides of
unknown toxicity /7/.
7.2.3 Conclusion
The data found is insufficient to construct a true toxicological profile of the
substance. Except for a certain degree of eye irritation, no trace of the
substance having harmful effects was found in the literature examined.
Based on the survey, 0-2% concentrations of the substance are expected to be
present in window colours. The limited toxicological data is insufficient to
evaluate the possible risks associated with the use of window colours by
children.
7.3
Toxicological profile of dimethyloxazolidine

7.3.1.1
Identification
Chemical name
EINECS name
CAS no.
Molecular
formula
Structural
formula
dimethyloxazolidine
4,4-dimethyloxazolidine
51200-87-4
C5H11NO
O
N
H
Applications
Preservative
Synonyms
The following synonyms have been the substance (8, 14):
4,4-dimethyl-1-oxa-3-aza-cyclopentane
4,4-dimethyl-1,3-oxazolidine
oxazolidine A
42
Regulation
The Danish EPAs guideline list for
self-classification
list
not classified
Xn;R22
permitted as preservative (max 0.1%)
not on the OEL list

Very little data was found on dimethyloxazolidine, cf. Tabel 7.3.
Tabel 7.3 Physico-chemical properties of dimethyloxazolidine.
- no data was found
Source
Physical form
101.2
Melting point (C)
Boiling point (C)
Log Kow
14

Without any specific reference to the underlying studies the US EPA
describes dimethyloxazolidine as being of mild acute toxicity upon ingestion,
skin contact and inhalation /9/.
We identified the following data on inhalation, ingestion and skin contact in
/8/.
Inhalation
3
The LC50 for inhalation by rats is recorded as 11,700 mg/m . This value does
not require classification under the Danish EPAs regulations.
Ingestion
LD50 for oral ingestion by rats is recorded as 950 mg/kg, which corresponds
to a self-classification as Harmful (Xn) with R22, Harmful if swallowed. This
corresponds with the classification on the guideline list for self-classification.
Skin contact
LD50 for skin contact with rabbits is recorded as 1,400 mg/kg, which
corresponds to a self-classification as Harmful (Xn) with R21, Harmful in
contact with skin.
43
The substance is described as a strong eye irritant /9/.

7.3.2.2 Subacute/chronic toxicity
The US EPA has stated that dimethyloxazolidine is not skin sensitizing and
that it does not result in damage to foetuses or newborn children. Information
from this source on mutagenicity is not accurate, though it does describe the
risks stemming from the substances mutagenic properties as being minimal
for humans in connection with the exploitation of the substances biocide
properties in e.g. drilling mud /9/.
7.3.3 Conclusion
Based on the relatively limited data, the substance is assessed as being harmful
to health through ingestion and skin contact and as being a strong eye irritant.
The hazards of ingestion are also reflected in the classification of the
substance on the Danish EPAs guideline list for self-classification.
Analysis results show concentrations of the substance between 0.0012 and
0.0075 % in three of the analysed products. At the these concentration, the
substance is not expected to constitute a problem in window colours.
7.4
Toxicological profile for ethylmethyl pyridine

7.4.1.1
Identification
Chemical name
EINECS name
CAS no.
Molecular
formula
Structural
formula
ethylmethyl pyridine
2-isopropyl pyridine
644-98-4
C8H11N
Application
Flavouring.
Synonyms
No synonyms were found for ethylmethyl pyridine.
Regulation
The Danish EPAs guideline list for selfclassification
Foodstuffs (the aroma list, 2002)
list
44
not classified
not assessed
not given
listed on the flavour list 2002
not on the OEL list

The small amount of available data on the physico-chemical properties of the
substance are shown in Tabel 7.4.
Tabel 7.4 Physico-chemical properties of ethylmethyl pyridine.
- no data was found
Source
Physical form
121.2
Melting point (C)
Boiling point (C)
Log Kow
2.26
14
22

No descriptions of the substances possible effects on human health were
encountered in the literature examined.
7.4.3 Conclusion
No data was found on which to base conclusions on the toxicological
properties of the substance.
0.059 % in one of the analysed products. The limited toxicological data is
insufficient to specifically evaluate the possible risks associated with the use of
window colours by children. However, the substance is not expected to
constitute a problem in such low concentration in window paints.
7.5
Toxicological profile for methylbenzene sulfonamide

7.5.1.1
Identification
Chemical name
EINECS name
CAS no.
Molecular
formula
methylbenzene sulfonamide
N-methylbenzenesulphonamide
5183-78-8
C7H9NO2S
Structural
formula
O
S
O
NH
45
Applications
Softener.
Synonyms
Methylbenzenesulfonamide has the synonym N(Phenylsulfonyl)methanamine /8/.
Regulation
list
not classified
not assessed
not given
not listed on the flavour list 2002
not on the OEL list

The physico-chemical properties of methylbenzene sulfonamide are shown in
Table 7.5.
Table 7.5 Physico-chemical properties of methylbenzene sulfonamide. - no data was found
Source
Physical form
powder
171.2
14
Melting point (C)
30
Boiling point (C)
202
0.095
22
Log Kow
0.92
22
9940
22

No descriptions of the substances possible effects on human health were
encountered in the literature examined.
7.5.3 Conclusion
0.097 % in one of the analysed products. The limited toxicological data is
insufficient to specifically evaluate the possible risks associated with the use of
window colours by children. However, the substance is not expected to
constitute a problem in low concentration in window paints.
46
7.6
Toxicological profile of methenamine

7.6.1.1
Identification
Chemical name
EINECS name
CAS no.
Molecular
formula
Structural
formula
methenamine
methenamine
100-97-0
C6H12N4
N
N
N
Applications
Preservative, also a food preservative. Formaldehyde releaser.
Synonyms
Methenamine has a large number of synonyms, including:
ammoform
ammonioformaldehyde
cystogen
formamine
formin
hEXA
hexaform
hexamethylene triamine
hexamethylenetetraamine
hexamine
hexilmethylenamine
hiprex
HMT
HMTA
mandelamine
methamin
resotropin
1,3,5,7-tetraazaadamantane
1,3,5,7-tetraazatricyclo[3.3.1.1(3,7)]decane
UREX
uritone
uroqid
urotropin
47
Regulation
F;R11 R42/43
not assessed
permitted as preservative (max
0.15%)
not on the OEL list

list
Migration limit from materials in contact
with food
15 mg/kg

The physico-chemical properties of methenamine are shown in Tabel 7.6.
Tabel 7.6 Physico-chemical properties of methenamine.
- no data was found
Source
Physical form
solid substance
140.2
14
Melting point (C)
280
14
Boiling point (C)
0.53
22
1.31
14
-4.15
22
490000
22
Log Kow

7.6.2.1
Toxicokinetic properties
Absorption
Following oral ingestion the substance is rapidly absorbed from the gastrointestinal tract /5/.
48
Metabolism
10-30% is hydrolysed at a relatively low pH in the gastric juices. Following
absorption the substance is distributed to the body, maximum serum
concentration being reached within an hour. The substance appears in the
urine within a few minutes and reaches a maximum within 1 to 3 hours.
Within 24 hours, 70-90% or more of a single dose of methenamine or one of
its salts is excreted intact in the urine through glomerular filtration or tubular
secretion. In acidic urine up to 20% of methenamine is hydrolysed to
ammonia and formaldehyde /8/. Methenamine is easily distributed to the
tissues and is absorbed into the breast milk /8/. No harmful effects on babies
during breast feeding have been reported /10/. The substance can also cross
the placenta barrier and has been observed in amniotic fluid of pregnant
women treated with the substance. Four hours after dosing the concentration
in the umbilical vein was equal to the mothers plasma level /11/. Only very
little methenamine decomposes in the blood and other tissues and the
substance is described as relatively systemically non-toxic. Toxicological
effects seem to be largely linked to the products of hydrolysis /10/.
7.6.2.2
Acute toxicity
Inhalation
No data
Ingestion
Studies of acute toxicity indicate that methenamine is of relatively low
toxicity. LD50 values of 9200 mg/kg body weight and above may be found in
the literature/11/. For humans, an acceptable daily intake is estimated at 0.5-5
g/kg /5/.
Skin contact
No data.
Studies of skin and eye irritation in rabbits (OECD guidelines were followed)
showed no irritant effects /11/. Very few details of these studies are given. In
several places in the survey literature, the substance is described as causing
irritation upon contact with the skin /12, 10/.
7.6.2.3

Studies of methenamine using the guinea pig maximization test on guinea
pigs showed the substance to be skin sensitizing. Nine out of ten animals used
in the test were sensitized /11/. Moreover, allergic eczema has been reported
on several occasions in industrial workers exposed to methenamine-containing
products /11/.
To study cross reactions with ethylenediamine, 32 ethylenediamine-sensitive
patients participated in a patch test in which they were exposed to
methenamine. One person showed a positive reaction to the test /11/.
Furthermore, it has been reported that methenamine-sensitized persons can
suffer asthma-like symptoms upon inhalation of methamine-containing fumes
/11/.
One cross-section study involved 17 industrial employees, 16 control subjects
and 4 out of 5 people who had retired from a methenamine-producing
49
company on medical grounds within the last ten years. On the basis of the test
it was concluded that high exposure can result in allergic contact eczema. It
was also concluded that there is no risk of respiratory sensitisation at average
3
methenamine concentrations of less than 1 mg/m /5/.
In the EU the substance is classified as sensitizing both upon skin contact and
inhalation.
Organ damage
In a test on rats, which were administered methenamine a) daily, oral gavage
(via stomach pump) for 90 days, b) daily, intramuscularly for 90 days and c)
repeated oral administration for 333 days (no further information),
respectively, the only reaction noted in the animals was a yellow colouration of
their fur. The doses administered were a) 400 mg/animal, b) 200 mg/animal
and c) 400 mg/animal, respectively. The yellow colouration of the fur was
caused by the reaction between the formaldehyde in their urine and the
kynurenine in the rats hair /11/.
In a two-year study on rats that received 50,000 ppm (approx. 2500
mg/kg/day) methenamine in their food showed no effects on food uptake,
weight increase or appearance and no histological changes were reported. The
test only included two males and three females and NOAEL was determined
at 2500 mg/kg /11/. In a two-year rat study using subcutaneous injections of
5000 mg/kg doses in 20 males and females, no treatment-related effects were
observed, except for the yellow colouration of the fur /11/.
Genetic damage
Various tests have been carried out to throw light on methenamines
mutagenic properties. The substance was examined in an Ames test using
various strains of Samonella Typhimurium, with and without metabolic
activation. The test results were largely negative, but a few positive tests were
also reported /13, 11/. Moreover, positive results have been reported from a
recombinant test on Bacillus Subtilis and a chromosome aberration test in
human HeLa cells. A cell transformation test in BHK cells was also positive,
as was a DNA repair test in E. coli P3478 (pol A-) at 6000 mg/plate. The
results are probably due to the release of formaldehyde. At 500 mg/plate
results were negative /11/.
Negative results were also reported in a gene mutation test in E. coli
WP2uvrA, in a mouse lymphoma test and in a chromosome aberration test in
human lymphocytes /11/.
A single in vivo test on Drosophila has shown mutagenicity in the larvae /11/.
An in vivo micronucleus study in mice found no clastogenic activity at 618,
206 or 69 mg/kg (LD50: 1853 mg/kg) after one-day and five-day exposure
and oral administration. In a dominant lethal test on mice which received
25,000 mg/kg orally there was a significant rise in dead implants. However,
because of the high dose, the results are doubtful. Another dominant lethal
test in mice which were administered doses of 8,000 10,000 mg/kg
intraperitoneally no induced lethal mutations were observed /11/.
In general, the studies referred to gave only scant information about the test
conditions.
Cancer
50
In tests on both mice and rats using methenamine no signs of carcinogenic

properties were found.
In a test on mice in which the substance (1.5% in chloroform) was applied to
the skin of the animals for 300 days no formations of malignant tumours were
observed. Nor where any treatment-related effects noted on Wistar rats that
were administered methenamine in their drinking water for 104 weeks. The
animals received doses of 1% and 5% respectively, in their drinking water.
50% of the animals in the high-dose group died within two weeks, whilst the
others recovered quickly. There was no sign of tumour activity /11/. A group
of Sprague Dawley rats were given continuous doses of 0.1% methenamine in
their drinking water with or without 0.2% NaNO2 for a period of 50 weeks.
This test also failed to produce any carcinogenic activity /11/.
In an 18-month study involving subcutaneous administration of methenamine
sarcomas were observed at the injection site in 8 of the 14 surviving animals.
Information about test conditions is limited /11/. Tumour formation was also
observed in another 12-18 month test on rats (15 males and 15 females)
which received subcutaneous injections of 1 ml 40% solution once a week.
Two spindle cell carcinomas, one alveolar mammary carcinoma, one
fibrosarcoma and two benign tumours were observed among the animals
treated. One malign tumour (blastoma) was observed in the control group.
There is no further data /11/.
In a three generation study involving Wistar rats which were daily
administered methenamine in their drinking water no signs of carcinogenic
effects were observed. The F1 and F2 generations received 1% in the water
until they were 40 weeks old. The F3 generation received doses until they
were 20 weeks old. A group of the offspring of the treated parents received
2% in their water for 50 weeks /11/.
The studies report that in the case of oral administration no carcinogenic
effects were demonstrated. In the case of subcutaneous injection isolated
tumours of various kinds were observed at the injection site. However, there
was no significant correlation with the treatment.
Several studies of reproduction toxicity in rats, which were administered
between 20 and 2500 mg/kg methenamine per day, in their food, in their
drinking water or via gavage (via stomach pump) respectively, failed to show
any significant effects on litter size, survival or postnatal weight increase. The
fertility of offspring was not effected nor were treatment-related histological
changes observed /11/. No NOAEL values were established in any of the
mentioned tests.
In a five generation study of rats, which received 5 or 50 mg/kg in their
drinking water no treatment-related changes were observed in test animals,
embryos or placenta. On the other hand, tumours were diagnosed in three of
the 48 rats in the high dose group /11/. There is no further data on the effects
/11/.
In a reproduction toxicity study on Beagles, the dogs were administered 600
or 1250 ppm (15 or 31 mg/kg/day) in their food. The animals were exposed
from day 4 to day 56 of the gestation period. No treatment-related effects on
gestation frequency or length, weight increase or litter size were observed. A
51
small rise in the number of stillborn puppies and a small decrease in body
weight and survival of offspring were observed in the high dose group. No
foetal damage effects were reported /11/.
A study of foetal damage in hens showed no effects on chick embryos or
foetuses /11/.
7.6.3 Conclusion
Methenamine is absorbed rapidly from the stomach and intestinal tract and
distributed to the tissues. The substance can penetrate the placenta barrier
and is also found in human beast milk. Studies indicate that methenamine is
of low acute toxicity upon ingestion. Information on irritant effects is scant.
Methenamine has been found to be skin sensitizing in both humans and
animals and human data has also been found that points to respiratory
sensitizing properties. In the EU the substance is classified as sensitizing upon
skin contact and inhalation.
Its genotoxic properties have been investigated in a number of tests which
have given both negative and positive results. The positive results in certain
studies may be due to the release of formaldehyde or extremely high doses.
Based on the data examined, the substance may be designated as a possible
weak mutagen, but further information is needed. Based on the literature
examined we encountered no documentation for carcinogenic effects or
effects deleterious to reproduction.
For humans, an acceptable daily intake is estimated at 0.5-5 g/kg /5/.
0.0013 % in one of the analysed products. Based on the study of industrial
workers, it is assessed that the substance will not result in either skin or
respiratory tract allergies in such low concentrations. It is unlikely that
children will ingest window colours in quantities that would result in the
exceeding of the ADI value.
7.7
Toxicological profile of dodecanthiol

7.7.1.1
Identification
Chemical name
EINECS name
CAS no.
Molecular
formula
Structural
formula
dodecanethiol
dodecane-1-thiol
112-55-0
C12H26S
SH
Applications
Plasticizer.
Synonyms
The following synonyms are used for dodecanthiol /14/:
lauryl mercaptan
1-dodecanethiol
52
n-dodecylmercaptan
n-lauryl mercaptan
1-mercaptododecane
Regulation
list
not classified
R43 N;R51/53
not given
listed on the flavour list 2002
not on the OEL list

The physico-chemical properties of dodecanethiol are shown in Tabel 7.7.
Tabel 7.7 Physico-chemical properties of dodecanethiol.
- no data was found
Source
Physical form
Melting point (C)
Boiling point (C)
liquid
14
202.41
22
-8
22
274
22
1.137
22
0.845
14
6.18
22
0.225
22
Log Kow
Water solubility (mg/L)

It is assumed that dodecanethiol will be oxidised and precipitated as sulphate.
In the unoxidized form the substance may potentially inhibit coenzyme Q,
which forms part of the cells energy metabolism and also acts as an
antioxidant.
Dodecanthiol is of relatively low toxicity if swallowed or inhaled /15/. An oral
LD50 value of 4225 mg/kg in mice and an intravenous LD50 in rats of >7000
mg/kg (no fatalities) are mentioned in the literature. The substance is also
reported as having a high sensitization potential and as causing irritation to
skin and eyes /15/. Chronic exposure, as has occurred in the footwear
industry, has resulted in skin irritation and sensitization.
7.7.3 Conclusion
Based on the extremely limited information, the substance may be presumed
to be of relatively low toxicity when swallowed or inhaled, to be irritating to
skin and eyes and to be potentially skin sensitizing. The latter property is
confirmed by the substances R43 classification in the Danish guideline list for
self-classification.
53

0.047 % in two of the analysed products. At such low concentrations, skin
sensitization is the primary problem. No data was found that would permit an
assessment of its sensitizing potential at a concentration of 0.047 %. However,
a single source states that the substance has high sensitizing potential.
7.8
Toxicological profile of 2-ethylhexylacrylate

7.8.1.1
Identification
Chemical name
EINECS name
CAS no.
Molecular
formula
2-ethylhexylacrylate
2-ethylhexyl acrylate
103-11-7
C11H20O2
Structural
formula
Applications
Paint binder and co-monomer in paints and dyes.
Synonyms
The following synonyms are used for 2-ethylhexylacrylate/14/:
acrylic acid 2-ethylhexyl ester
EHA
2-ethylhexyl 2-propenoate
2-ethylhexyl propenoate
1-hexanol, 2-ethyl-, acrylate
octyl acrylate
2-propenoic acid 2-ethylhexyl ester
2-propenoic acid octyl ester
Regulation
list
Xi;R37/38 R43
not assessed
not given
not on the OEL list

The physico-chemical properties of 2-ethylhexylacrylate are shown in Tabel
7.8.
54
Tabel 7.8 Physical/chemical properties of

2-ethylhexylacrylate.
Source
Physical form
liquid
21
184,3
22
Melting point (C)
-90
22
Boiling point (C)
213,5
22
23,7
22
0,89
21
Log Kow
4,09
22
100
22

7.8.2.1
Toxicokinetic properties
Absorption
No data,
Metabolism
Following intraperitoneal administration most of the 2-ethylhexylacrylate is
rapidly metabolised and the C14 labelled substance was distributed mainly to
the liver, kidneys and lungs. Elimination from the bloodstream takes place in
two stages, where the half-life for the first stage in young rats is 30 or 60
minutes following intravenous or intraperitoneal administration, respectively,
and for older rats about 2 hours. The half-life during the slow stage is 6 or 14
hours for young and old rats, respectively /11/. More than half of 2ethylhexylacrylate is exhaled as carbon dioxide. Exhalation of unchanged 2ethylhexylacrylat was 0.05% (i.v.) and 0.3% (i.p.) respectively, and 14% (i.v.)
and 7% (i.p.) was secreted in the urine. Over 72 hours, a greater percentage of
intraperitoneally administered substance is exhaled than when administered
orally /11/.
7.8.2.2
Acute toxicity
Inhalation
In rats, 8 hours inhalation of a saturated atmosphere caused no fatalities /11/.
LC50 in mice is reported as being greater than 7713 mg/l after 30 minutes
exposure and LCLo in mice as being 600 mg/l /11/.
Inhalation of concentrated fumes induces lethargy and spasms in humans /8/.
Ingestion
Studies with rats have reported LD50 values down to 1540 mg/kg in /8/ and
between 4435 mg/kg and 12,800 mg/kg body weight in /11/. The majority of
figures are around 5600 mg/kg body weight.
Skin contact
Dermal LD50 in rabbits has been reported from >700 mg/kg to 14,192 mg/kg
body weight. The value for rats has been given at >12,000 mg/kg /11/.
Frequent reference is made to values around 8500.
55

Undiluted 2-ethylhexylacrylate has been found to be irritating to the skin in
trials with rabbits and mildly irritating in contact with rabbit eyes /8, 11/.
The substance is classified as irritating to respiratory organs and skin on the
List of Dangerous Substances.
7.8.2.3

2-ethylhexylacrylate has shown sensitizing effects in both sensitization tests on
guinea pigs and in patch tests on humans /11/. The substance is also classified
as R43, May cause sensitization by skin contact, on the List of Dangerous
Substances. Cross allergy with methylmethacrylate has been reported /11/.
Organ damage
Repeated dosing of rats through inhalation of concentrations of respectively 1
mg/l and 0.375 mg/l for 2.5 weeks, 6 hours/day, 5 days/week produced no
toxic effects at the lower dose. At the higher dose the beginning signs of
weight loss, drowsiness and laboured breathing were observed. There was no
change in the blood picture and autopsies revealed no signs of pathological
changes /11/. In a corresponding study covering 90 days using doses of
respectively 0.075 mg/l, 0.225 mg/l and 0.75 mg/l there were no fatalities and
no toxic effects at the lower dose. The animals in the highest dose group
showed signs of mild drowsiness, closed eyelids during exposure and retarded
physical development. Increased liver test figures and degeneration of the
olfactory epithelium in the nasal fossae were also observed. At 0.225 mg/l the
same effects were observed as at the highest dose but to a considerably lesser
degree and without impact on the liver test figures /11/. In one 4-month study
involving rats no effects were observed at a dose of 0.359 mg/l administered 5
hours/day /11/.
Dermal exposure of mice for periods of between 12 days and three months
produced no systemic effects but primarily irritation effects on the site of
application /11/. Daily application of 1 ml on the skin of rabbits for 2.5 weeks
produced serious skin changes (inflammation, necrosis and ulcer formation)
and treatment had to be terminated after 12 applications /11/.
Genetic damage
2-ethylhexylacrylate has been tested using the Ames' test on several strains of
Salmonella Typhimurium with and without metabolic activation with negative
results. A HGPRT assay for point mutations in mammal cells (CHO) was
also negative. Cell transformation tests in fibroblast cells from C3H-mouse
embryos and micro-nuclear tests on mouse L5178Y lymphoma cells were also
negative /11/.
On the other hand, unambiguous results were not obtained in gene mutation
tests with L5178Y mouse lymphoma cells, in sister chromosome exchange
tests in CHO cells and in Unscheduled DNA synthesis in primary rat liver
cells /11/. There is no detailed information on these tests.
In an in vivo cytogenetic test in mice, which were dosed orally once a day or
five times in five days to 2500 mg/kg, exposure produced toxic effects on the
animals but did not produce chromosome aberrations in the bone marrow
/11/.
56
Cancer
In a study involving dermal lifetime exposure of male mice to concentrations
of 2.5%, 21%, 43% (only 24 weeks) and 86.5% in acetone, papillomas and
other skin tumours were observed on the skin treated after 11 months. The
authors conclude that the skin tumours could be a consequence of the
irritative properties of the substance /11/. Another 2-year study using male
mice also failed to show direct signs of any carcinogenic potential for the
substance /11/.
The International Agency for research on Cancer (IARC) has assessed the
substance and placed it in group 3, which includes substances not classifiable
as to their carcinogenicity in humans due to the lack of data /8/.
No data.
7.8.3 Conclusion
Investigations into 2-ethylhexylacrylate indicate that the substance is rapidly
metabolised and is expelled mainly in the exhalation air. The acute toxicity of
the substance may be assumed to be low, but one place in the literature quotes
an oral LD50 value that would involve classification of the substance under
R-phrase R22, Harmful if swallowed. This value deviates from the levels most
frequently referred to and is thus not considered relevant. 2-ethylhexylacrylate
has been found to be irritating to skin and mildly irritating to the eyes. The
substance is classified as a skin and respiratory irritant. 2-ethylhexylacrylate
has shown sensitizing effects in both sensitization tests on guinea pigs and in
patch tests on humans. In the EU the substance is classified as sensitizing and
assigned risk phrase R43, May cause sensitization by skin contact.
Results of mutagenicity studies are largely negative, but a single test to
measure the effects on DNA failed to produce unambiguous results. Tests on
mice have found no direct signs of the substance having carcinogenetic
potential. The IARC has assessed the substance and placed it in group 3,
which includes substances not classifiable as to their carcinogenicity in
humans due to the lack of data. No data was found on reproduction toxic
effects.
0.018 % in nine of the analysed products. At such low concentrations skin
sensitization is the primary problem associated with the identified
toxicological properties. Data was not found that would permit an evaluation
of sensitization potential at a concentration of 0.018 %, which is, however,
considerably below the Classification Statutory Orders general de minimis
limit of 1 % for products containing sensitizing substances.
57
7.9
Toxicological profile of pigment red 146

7.9.1.1
Identification
Chemical name
EINECS name
CAS no.
Molecular
formula
pigment red 146

N-(4-chloro-2,5-dimethoxyphenyl)-3-hydroxy-4-[[2methoxy-5-[(phenylamino)carbonyl]
phenyl]azo]naphthalene-2-carboxamide
5280-68-2
C33H27ClN4O6
Structural
formula
Applications
Pigment.
Synonyms
The following synonyms were found for Pigment red 146:
2-Naphthalenecarboxamide, N-(4-chloro-2,5-dimethoxyphenyl)-3hydroxy-4-[[2-methoxy-5-[(phenylamino)carbonyl]phenyl]azo] C.I. 12485
Permanent Pink FBB
Regulation
Authority' s occupational exposure limit
list
58
not classified
not assessed
not permitted
not on the OEL list

The physico-chemical properties of Pigment red 146 are shown in
Table 7.9. Physico-chemical properties of Pigment red 146.
Table 7.9. Physico-chemical properties of Pigment red 146.
*based on QSAR. - no data was found.
Source
Physical form
solid
24
611,1
Melting point (C)
320
Boiling point (C)
880*
1,42
Log Kow
16
1.49 E-05*

7.9.3 Conclusion
No information was found on constituent concentrations during the survey,
which taken together with the limited toxicological data also makes it difficult
to specifically evaluate the possible risks associated with the use of window
colours by children.
7.10 Toxicological profile of pigment yellow 138
7.10.1
Identification of the substance and physical-chemical properties
7.10.1.1 Identification
Chemical name
EINECS name
CAS no.
Molecular
formula
pigment yellow 138

3,4,5,6-tetrachloro-N-[2-(4,5,6,7-tetrachloro-2,3-dihydro1,3-dioxo-1H-inden-2-yl)-8-quinolyl]phthalimide
30125-47-4
C26H6Cl8N2O4.
O
N
Structural
formula
Cl
O HO
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Applications
Pigment.
59
Synonyms
The following synonyms were found for Pigment yellow 138:
1H-Isoindole-1,3(2H)-dione, 4,5,6,7-tetrachloro-2-[2-(4,5,6,7tetrachloro-2,3-dihydro-1,3-dioxo-1H-inden-2-yl)-8-quinolinyl] C. I. 56300
Quinophthalone yellow.
Regulation
list
not classified
not assessed
not permitted
not on the OEL list

The physico-chemical properties of the substance are shown in Table 7.10.
Table 7.10. Physico-chemical properties of Pigment yellow 138.
- no data was found.
Source
Physical form
solid
25
694,0
25
Melting point (C)
Boiling point (C)
2,02
Log Kow
7.10.2
25
insoluble
25
Toxicological properties

7.10.3
Conclusion

No information was found on constituent concentrations during the survey
which taken together with the limited toxicological data also makes it difficult
to specifically evaluate the possible risks associated with the use of window
colours by children.
7.11
Summary
Table 7.11 summarises the substances intrinsic properties with regard to the
key parameters: acute effects, local effects, sensitization, the effects of
60
repeated exposure, and carcinogenicity(C), mutagenicity (M), and

reproduction toxicity (R). Moreover, the most highly critical effects of the
substances have been listed based on the available data.
Table 7.12 summarises information about regulatory requirements applying
to the substances together with specification of concentrations of those
substances identified through chemical analysis. Information about dioxazine
originates from one producer and specifies typical contents of the substance in
window colours.
Common to all the substances is the fact that the content percentages found in
the survey and through chemical analysis respectively are lower than the levels
at which known health harmful effects can be expected to occur in connection
with the use of window colours.
61
Table 7.11 List of toxicological properties and critical effects of the ten substances
Positive test results/data, Negative test results/data, and no data. Exposure pathways are specified as follows: I =
ingestion, S =skin contact, E = eyes, R = respiratory organs.
Name of substance
CAS no.
Acute
effects
Local
effects
Sensitization
Repeated
exposure
I
CMR
Critical effects
M R
1-Naphthol
90-15-3
- -
- - -
Dioxazine
6358-30-1
- -
- -
Dimethyloxazolidine
51200-87-4
- -
- - -
644-98-4
- - -
- - -
- -
- - -
- - -
No data
5183-78-8
- - -
- - -
- -
- - -
- - -
No data
Methenamine
100-97-0
- -
- -
Dodecanethiol
112-55-0
- -
- - -
Sensitization
(S,R)
Sensitization (S)
103-11-7
- -
Pigment red 146
5280-68-2
- - -
- - -
- -
- - -
- - -
No data
Pigment yellow 138
30125-47-4
- - -
- - -
- -
- - -
- - -
No data
62
Harmful to health
(I,S)
Eye irritation
Acute toxicity (I,S)
Sensitization (S)
Table 7.12 List of regulations applying to the ten substances.

Name of substance
CAS no.
Conc.
(%)
1-Naphthol
90-15-3
Dioxazine
6358-30-1
0-2
Dimethyloxazolidine
51200-87-4
644-98-4
5183-78-8
Methenamine
Classification)
Max. permissible
value in work
environment
Cosmetic Statutory
Order
The
positive list
The
Flavour
List 2002
Xn;R21/22
Xi;R37/38-41
Not specified
No
Max. 2.0% in hair dye
No
No
No
No
No
0.00120.0075
0.0580.059
0.0850.097
Xn;R22
No
No
No
Not specified
No
Permitted in products
in short-term contact
with the skin
Permitted as
preservative, max 0.1%
Not specified
No
No
Not specified
No
Not specified
No
No
100-97-0
0.000120.0013
F;R11 R42/43
No
No
No
Dodecanthiol
112-55-0
R43 N;R51/53
No
No
No
103-11-7
Xi;R37/38 R43
No
Not specified
No
No
Pigment red 146
5280-68-2
0.000290.047
0.00130.018
-
Permitted as
preservative, max
0.15%
Not specified
Not specified
No
Not permitted
No
No
Pigment yellow 138
30125-47-4
Not specified
No
Not permitted
No
No
1) Classifications form the List of Dangerous Substances are specified in bold type and
classifications from the Danish EPAs guideline list for self-classification are specified in normal
type.
63
8 References
1
MST (www.mst.dk/kemi/0250102.htm).
Heller, E. 2001. Chairman of the Danish Joint Council for Creative

and Hobby Materials. Personal communication.
The Danish EPA 1999. Environmental parameters relative to

flexographic printing. Environmental project no. 482.
Ulmann 2001. Ullmann's Encyclopedia of Industrial Chemistry, 6th

Edition. CD-ROM.
TOXLINE: http://toxnet.nlm.nih.gov/cgibin/sis/htmlgen?TOXLINE.
Danish EPA 1998. Survey of Azo-colorants in Denmark:

Consumption, use, health and environmental aspects.
Environmental project no. 509.
EPA: http://www.pestlaw.com/x/registration/EPAInert_Lists.html#LIST%201.
Chembank: HSDB and RTECS online search, 21 May 2002.
http://www.epa.gov/oppsrrd1/REDs/factsheets/3095fact.pdf.
10
HSDB-web: http://sis.nlm.nih.gov/cgi-bin/sis/htmlgen?HSDB.
11
European Commission, Joint Research Centre (2000): International

Uniform Chemical Information Database. IUCLID CD-ROM,
Existing Chemicals Year 2000 edition.
12
Lewis, RJ. SAX's Dangerous Properties of Industrial Materials, 10

Ed., New York: Van Nostrand Reinhold, 2000.
14
Chemfinder. http://chemfinder.cambridgesoft.com/.
15
Clayton, G.D. and Clayton, F.E. (eds). Patty's Industrial Hygiene

and Toxicology, vol 2A, New York Wiley: Wiley, 1978.
16
SCCNFP/0130/99, final. Opinion Of The Scientific Committee On

Cosmetic Products and Non-Food Products Intended for
Consumers concerning 1-naphtol.
http://europa.eu.int/comm/food/fs/sc/sccp/out138_en.pdf.
64
th
Other literature and databases consulted:
17
http://skychem.com/colordata/pr146.htm.
18
European Chemical Bureau: http://ecb.ei.jrc.it/existing-chemicals/.
19
MEDLINE: http://medlineplus.gov/.
20
IRIS: http://toxnet.nlm.nih.gov/cgi-bin/sis/htmlgen?IRIS.
21
CCRIS: http://toxnet.nlm.nih.gov/cgi-bin/sis/htmlgen?CCRIS.
22
GENETOX: http://toxnet.nlm.nih.gov/cgi-bin/sis/htmlgen?CCRIS.
23
Physprop. The Physical Properties Database (PHYSPROP)

http://esc.syrres.com/interkow/physdemo.htm.
24
http://www.navpadpigments.com/.
25
European colour (pigments) Ltd. 1998. Safety sheet for Pigment

Red 146.
26
BASF Corporation 2001. Safety sheet for PALIOTOL Yellow L

0962 HD.
27
Madsen, T. and Larsen, J. R. Milj- og sundhedsvurderinger af

hndsbe, (Environmental and health evaluation of toilet soap)
Technical announcement no. 12, 1998, pages 32-33.
28
Danish EPA 2003. List of Dangerous Substances. Statutory Order

no. 439 of 3/6 2002 on the List of Dangerous Substances.
29
Danish EPA 2001. Environmental and Health Assessment of

Substances in Household Detergents and Cosmetic Detergent
Products. Environmental project no. 615.
30
The Danish Working Environment Servcie 2000. At-vejledning

C.0.1. October 2000. Grnsevrdier for stoffer og materialer
(Maximum Permitted Values for substances and Materials).
31
Danish EPA 2000. The Ministry of Environment and Energys

Statutory Order no. 594. of 6 June 2000 on Cosmetics Products.
Cosmetics Statutory Order).
32
The Positive List: list of food additives, 2000

http://www.vfd.dk/publikationer/publikationer/publikationer/positiv2
000/.
33
Danish EPA 2001. Guideline List for Self-Classification of

Hazardous Substances.
http://www.mst.dk/default.asp?Sub=http://www.mst.dk/presse/sol/16
020000.htm.
65
34
EU 2002,
Flavourlisten.http://www.vfd.dk/diverse/flavour/flavourstoffer/flavou
rlisten2002.pdf.
35
International Agency for Research on Cancer (IARC). IARC

monographs database. http://monographs.iarc.fr/.
36
Danish Consumer Agency 1995. Statutory Order no. 329 of

23.5.1995 on Safety Requirements for Toys and Products which by
Virtue of their Outer Appearance Might be Mistaken for Food
Products.
66

Pigment Identification

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Pigment Identification

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Survey of chemical substances in

Survey and assessment of chemical

Sonja Hagen Mikkelsen, Sven Havelund and Anders Skibsted

SURVEY OF MANUFACTURERS AND SUPPLIERS

4 SURVEY OF CONSTITUENT SUBSTANCES IN WINDOW

SELECTED SUBSTANCES AND DATA SEARCHING

2 COMPOSITION OF AND TYPICAL CONSTITUENT

TOXICOLOGICAL PROFILE OF SELECTED SUBSTANCES

7.1.2 Toxicological properties

Chemical Abstracts Service Registry number

Hazard symbols and R-phrases used

Summary and conclusions

ACMI: Art & Creative Materials Institute, Inc.

Pigment red 146

Pigment yellow 138

Of the 10 substances investigated, three are included on the List of Dangerous

Exposure to substances contained in the products may occur by direct contact

2 Composition of and typical

A brief description of the four types of constituent substance is given below.

Primary pigments give whiteness or colour to the product. Typically, titanium

3 Survey of manufacturers and

European manufacturers dominate the Danish market. Worldwide there are

Lacufa AG, Nerchau Mal- und

Palmer Paint Products

Schjerning Farver A/S

Table 3.2 Selected Danish window paint suppliers.

Pbo Color Scandinavia ApS

Crystal Clear window color

Fun & Easy

Fun & Fancy

Funny Window Color

Gallery Glass Window Color

Mak'easy window color

4 Survey of constituent substances

Carbon black (C)

Name of substance (formula)

Pigment red 101

4,4'- (3,3'-dichloro 1,1'-biphenyl

N-(4-chloro-2,5dimethoxyphenyl)-3-hydroxy-4[[2-methoxy-5Pigment red 146

N-(5-chloro-2-methylphenyl)-3hydroxy-4-[[2-methoxy-5[(phenylamino)carbonyl]phenyl Pigment red 147

3,4,5,6-tetrachloro-N-[2(4,5,6,7-tetrachloro-2,3-dihydro1,3-dioxo-1H-inden-2-yl)-8Pigment yellow 138

None of the pigments appear on the List of Dangerous Substances or the

Acrylates and polyurethane polymers are used as paint binders in window

Acrylic acid (C3H4O2)

MW= Molecular Weight; S = Solubility in water;

According to the information gathered, window colours contain a number of

Triethylene glycol (C6H14O4)

Propylene glycol (C3H8O2)

The two isothiazolinone derivatives are both contained by window colours in

5.2.1 GC/MS screening (extractable organic substances)

5.3.1 GC/MS screening (extractable organic substances)

5.3.1.1 X-ray analysis

5.3.1.2 Water content

Tabel 5.6 Results of water analysis of V6-V10. Results are given in %.

The screening analysis of constituent substances in window paints generally

Table 5.7 Substances selected for toxicological assessment.

6 Selected substances and data

Basis for the selection of substances

The selected substances

Pigment red 146

Pigment yellow 138

Data on the physico-chemical properties and the health implications were

Pigment red 146

Pigment yellow 138